Bonding and metastability for Group 12 dications

Electronic structure and bonding properties of the Group 12 dications M₂ ²⁺ (M = Zn, Cd, Hg) are investigated and electron density-derived quantities are used to characterize the metastability of these species. Of particular interest are the complementary descriptions afforded by the Laplacian of the electron density ∇² ρ(r) and the one-electron Bohm quantum potential (Q =  $$ ) along the bond path. Further, properties derived from the pair density including the localization-delocalization matrices (LDMs) and the interacting quantum atoms (IQA) energies are analyzed within the framework of the quantum theory of atoms in molecules (QTAIM). From the crossing points of the singlet (ground) and triplet (excited) potential energy curves, the barriers for dissociation (BFD) are estimated to be 25.2 kcal/mol (1.09 eV) for Zn₂ ²⁺ , 22.8 kcal/mol (0.99 eV) for Cd₂ ²⁺ , and 26.4 kcal/mol (1.14 eV) for Hg₂ ²⁺ . For comparison and benchmarking purposes, the case of N₂ ²⁺ is considered as a texbook example of metastability. At the equilibrium geometries, LDMs, which are used here as an electronic fingerprinting tool, discriminate and group together Group 12 M₂ ²⁺ from its isoelectronic Group 11 M₂ . While "classical" bonding indices are inconclusive in establishing regions of metastability in the bonding, it is shown that the one-electron Bohm quantum potential is promising in this regard.